탄산에틸렌-아세톤 혼합용액에서의 1-1 전해질의 전기전도도

김시중,신영국,Si-Joong Kim,Young-kook Shin 대한화학회 1983 대한화학회지 Vol.27 No.3

The conductances of sodium, potassium, ammonium, tetramethylammonium, and tetraethylammonium iodides, picrates(Pic) of sodium and potassium, and tetrabutylammonium tetraphenyl-boride have been measured in ethylene carbonate-acetone mixtures at $25{\circ}C$. The limiting equivalent conductances of the electolytes were computed by Fuoss-Kraus equation and the order was $(C_4H_9)_4NB(ph)_4<NaPic<HPic<NaI<KI<NH_4I(C_2H_5)_4NI<(CH_3)_4NI$ at any composition of the mixtures. The dissociation constants of the salts showed that the mixtures are good ionizing solvents for the salts. The order of limiting ionic equivalent conductance, $Na^+<K^+<NH_4^+$, is consistent with exactly the reverse order found for solvation number. Effective solvated radii calibrated by the Nightingale method showed that picrate ion seems to be unsolvated and that iodide ion seems to be solvated to some extent in the mixtures. 비양성자성 극성용매인 탄산에틸렌과 아세톤과의 혼합용매에서 NaI, KI,$ NH_4I,\;(CH_3)_4NI,\;(C_2H_5)_4NI$, NaPic(Pic:피크린산이온), KPic, $(C_4H_9)_4NB(ph)_4$의 전기전도도를 $25{\circ}C$에서 측정하였다. 한계당량전도도를 Fuoss-Kraus식에 의하여 구한 결과 그 크기의 순위는 혼합용매의 성분비에 관계없이 $(C_4H_9)_4NB(ph)_4<NaPic<HPic<NaI<KI< NH_4I(C_2H_5)_4NI<(CH_3)_4NI$이었다. 이 전해질들의 해리상수로 부터 탄산에틸렌-아세톤 혼합용매는 이들에 대하여 좋은 이온화용매임을 알 수 있었다. 한계이온당량 전도도의 순위, $Na^+<K^+<NH_4^+$는 용매화수의 역순위와 일치하였다. Nightingale 방법에 의하여 구한 각 이온의 유효 용매화반지름에 의하면 피크린산이온은 용매화되어 있지 않으며, 요오드화이온은 탄산에틸렌-아세톤 혼합용매에서 상당히 용매화되어 있음을 알 수 있었다.

Metal Cupferrate Complex 에 關한 硏究 (第 3 報) $H_2O$-Chloroform 系에서의 Hydrogen Cupferrate 의 分配係數에 關한 硏究

김시중,신두순,Si-Joong Kim,Doo-Soon Shin 대한화학회 1963 대한화학회지 Vol.7 No.4

$H_2O$-chloroform系에서의 hydrogen cupferrate의 分配係數와 水溶液相의 pH, 이온强度 및 cupferron의 濃度와의 關係를 살폈는데, 分配係數는 pH(1.50∼3.00사이)와 이온强度(0.1∼2.0사이)에는 無關하지만 cupferron의 濃度가 커질수록 分配係數는 增加했으며, 熱力學的인 分配係數의 完全한 값으로 120.0이란 새로운 값을 얻었다. 한편 cupferron의 濃度가 커짐에 따라 分配係數가 增加하는 까닭은 chloroform相에 monomer로서의 HCup. 의 活動度의 감소로 간주하고, chloroform相에서의 HCup. 의 濃度와 chloroform相에서의 HCup. 의 活動度係數와의 關係를 表示하는 實驗式 $-logf_{CHCl3}=0.1285C_{CHCl3}+{7.775C^2}_{CHCl3}$를 얻었으며, 이 式은 HCup. 의 chloroform 溶液 0.1mole/l order 以下의 濃度에서 大端히 잘 맞는다. The distribution ratio of hydrogen cupferrate in $H_2O-CHCl_3$ system was considered as a function of pH ($HClO_4$), ionic strength ($NaClO_4$), and cupferron concentration in perchloric acid media, respectively. The values were independent upon pH (1.50∼3.00 range) and ionic strength (0.1∼2.00 range), but they increased as increasing the cupferron concentration in the acidic media. At the infinite dilution, the thermodynamic distribution ratio between chloroform and aqueous phase was 120. 0. The activity coefficients of hydrogen cupferrate in chloroform solution were determined by the distribution ratio. This activity coefficient may be calculated by using the empirical equation, $-log\;f_{CHCl3}=0.1285C_{CHCl3}+{7.775C^2}_{CHCl3}$ which represents the experimental data quite well for the solution in 0.1 mole/l order of hydrogen cupferrate concentration.

물아닌 용액에서의 용질의 행동에 관한 연구 (제2보). 요소, 1,3-디메틸요소, 아세트아미드와 프로피온아미드의 상대점도와 삼투계수

김시중,신영국,Si-Joong Kim,Young-Kook Shin 대한화학회 1980 대한화학회지 Vol.24 No.3

요소 1,3-디메틸요소(DMU), 아세트아미드, 프로피온아미드의 상대점도와 삼투계수를 dimethylsulfoxide(DMSO), 메탄올, 에탄올 및 물용액에서 $25^{\circ}$C와 $45^{\circ}$C에서 각각 측정하였다. 수용액에서 각 용질의 점도증가량은 분몰랄부피가 증가하면서 증가하였으나 물아니 용액에서는 오히려 감소하였다. 또한 요소의 점도 증가량은 수용액에서는 DMU보다 작았으나, 물아닌 용액에서는 DMU보다 컸다. 그러나 아미드류는 어느 용매에서나 거의 같은 점도증가량을 나타내었다. 요소수용액에서 삼투계수는 DMU 수용액보다 컸으며, 물아닌 용액에서 요소용액은 DMU보다 Raoult의 법칙에서 크게 벗어났다. 이러한 사실로부터 요소는 DMSO 용액에서 자체회합을 크게 일으키고 있으며 알코올용액에서는 DMU보다는 큰 정도의 용매-용질상호작용, 수용액에서는 용매구조를 파괴하고 있음을 알았다. 아세트아미드나 프로피온아미드는 수용액이나 DMSO 용액에서보다 알코올용액에서 더 크게 용매구조를 파괴하고 있음을 알았다. The relative viscosities and osmotic coefficients of solutions of urea, 1,3-dimethyl-urea(DMU), acetamide(AA), and propionamide (PA) in dimethylsulfoxide(DMSO), water, methanol, and in ethanol have been measured at 25 and $45^{\circ}$C by viscometry and osmometry. Viscosity increment in nonaqueous solutions decreased with increasing of the partial molal volumes of the solutes, but in aqueous solution the result was inversed. Viscosity increment of aqueous solution was smaller than that of aqueous DMU solution, but that of nonaqueous urea solution was larger than that of DMU. Amides, however, showed similar viscosity increment in any solvent.Osmotic coefficients of aqueous solution of urea were larger than those of DMU. In the nonaqueous solutions urea exhibited larger deviation from Raoult's law than DMU. The results indicated that urea molecules break water-structure in water, self-associate in DMSO, and showed larger solute-solvent interaction in alcohols than DMU. It can be also confirmed that amides break alcohol structure to a greater extent than any other solutes.

물, Dioxane-물 및 Ethanol-물의 混合溶媒에서의 Hydrogen Cupferrate의 酸解離常數의 決定

김시중,윤창주,장인순,Kim, Si-Joong,Yoon, Chang-Ju,Chang, In-Soon 대한화학회 1966 대한화학회지 Vol.10 No.3

The glass electrode was empirically calibrated in dioxane-and ethanol-water mixed solvents, by means of which the pH-meter reading could be converted to stoichiometric hydrogen ion concentration. By the potentiometric titration method, the thermodynamic dissociation constants of hydrogen cupferrate (HCup) with variations of ionic concentration in aqueous solution were determined, and by the extrapolation of the constants the new thermodynamic $pK_a$ value, 3.980${\pm}$0.006, at zero ional concentration was obtained. The thermodynamic dissociation constants of HCup in dioxane-and ethanol-water solution were also potentiometrically determined with the changes in composition of organic solvents at 0.01 and 0.05 of the ionic strength(${mu}$) and 25 $^{\circ}C$. The empirical formula of the constants with mole fraction(n) of the organic solvent are as follow: Dioxane-water solution. $pK_a$= 12.96n + 4.10 at ${\mu}$ = 0.01, n = 0.0228∼0.171 $pK_a$= 12.05n + 4.23 at ${\mu}$ = 0.05, n= 0.0228∼0.171 Ethanol-water solution, $pK_a$= 4.0ln + 4.26 at ${\mu}$= 0.01, n= 0.0395∼0.262 $pK_a$= 3.83n + 4.34 at ${\mu}$= 0.05, n= 0.0395∼0.262

물아닌 용매에서 Dibenzo-18-Crown-6 화합물과 알칼리토금속이온이 이루는 착물의 안정도상수

김시중,고석노,신영국,윤창주,Si-Joong Kim,Seok-Ro Koh,Young-Kook Shin,Yoon Chang-Ju 대한화학회 1983 대한화학회지 Vol.27 No.3

알칼리토금속이온과 dibenzo-18-crown-6이 디메틸술폭시드, 디메틸포름아미드, 아세토니트릴용매에서 이루는 착물의 안정도상수를 일정한 이온세기에서 $25{\circ}C$와 $35{\circ}C$에서 전기전도도법으로 각각 구하였다. 안정도상수의 순위는 모든 용매에서 $Ca^{2+}<Sr^{2+}< Ba6{2+}$이었다. 그 크기는 용매의 염기도에 역으로 비례하였다. 이러한 결과를 이온-공동의 상대적 크기, 용매의 염기도 및 용매화 현상으로 설명하였다. The stability constants for the complexes formed between dibenzo-18-crown-6 compound and alkaline earth metal cations in dimethylsulfoxide, dimethylformamide, and acetonitrile have been obtained by conductometry at $25{\circ}C\;and\;35{\circ}C$respectively. The stability constants were increased in order of $Ca^{2+}<Sr^{2+}<Ba6{2+}$ in any solvent, and the magnitudes were found to be reversely proportional to the solvent donicities. The result could be understood in terms of ion-cavity radius concept, solvent basicity, and solvation of the cations.

($Ba_{1-$\chi$}Pb_$\chi$$)TiO3 세라믹의 구조와 전기적 특성

김시중,김건,박휴범,안병준,Kim, Si-Joong,Kim, Keon,Park, Hyu-Bum,Ahn, Byeung-Joon 한국세라믹학회 1992 한국세라믹학회지 Vol.29 No.4

The crystal structures and the bonding characteristics in (Ba$\chi$Pb1-$\chi$)TiO3 have been investigated by X-ray diffraction analysis and infrared spectrophotometry. As Ba2+ ion in BaTiO3 were substituted by Pb2+ ion, the structures were changed to orthorhombic from tetragonal, and also the covalent character in Ti-O bond increased, and then the dielectric constants decreased gradually. In the mixed oxide containing Pb2+ ion more than 50%, the change-transfer energy of titanium ion increased.

Metal Cupferrate Complex 에 關한 硏究 (第 2 報) Spectrophotometry 에 의한 Fe(III)-Cupferrate의 化學組成의 決定

김시중,신두순,Si-Joong Kim,Doo-Soon Shin 대한화학회 1963 대한화학회지 Vol.7 No.4

Spectrophotometry에 의한 몰比法, 運續變化法 및 傾科比法으로 chloroform phase에 存在하는 Fe(III)-cupferrate의 組成을 決定하였는데, 그 황化合物은 325m$\mu$에서와 385m$\mu$에서 모두 $FeCupf_3^인 化學式을 갖는 것이었다. Fe (III)-cupferrate composition in chloroform phase was determined by molar ratio method, continuous variation method and slope ratio method spectrophotometrically at 325m$\mu$ and 385m$\mu$ wavelength. At both wavelength, compositions of the complex were Fe$Cupf_3$.

전이 및 중금속이온과 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxa-cyclooctadecane과의 착물형성

김시중,이명재,구창현,우경자,Kim, Si-Joong,Lee, Myung-Jae,Koo, Chang-Hyung,Woo, Kyoun-Ja 대한화학회 1991 대한화학회지 Vol.35 No.6

몇 가지 전이금속이온(Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ)) 및 후전이금속이온(Cd(Ⅱ), Hg(Ⅱ), Pb(Ⅱ))과 $N_2O_3$계 거대고리 리간드인 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane 사이에 형성되는 착물의 안정도 상수를 수용액에서 전위차 적정법으로 결정하였다. 각 착물의 안정도 상수$(logK_f)$는 $25^{\circ}$C에서 Co(Ⅱ): 3.83, Ni(Ⅱ) : 4.56, Cu(Ⅱ) : 7.74, Zn(Ⅱ) : 4.98, Cd(Ⅱ) : 3.91, Hg(II) : 14.87, Pb(Ⅱ) : 6.65이었다. 전이금속착물의 안정도 순위는 Williams-Irving 서열인 Co(Ⅱ) < Ni(Ⅱ) < Cu(Ⅱ) < Zn(Ⅱ)와 일치하였고, 후전이금속착물의 안정도는 Cd(Ⅱ) < Pb(Ⅱ) < Hg(Ⅱ)이 순위이었다. 한편 메탄올 용액에서 자외-가시선이온과 리간드가 1:1인 조성을 가졌으나, Ni(Ⅱ), 착물은 1:1과 1:2 두 가지 조성을 가질 수 있음을 알았으며, 또 디메틸술폭시드 용액에서 $^1H-$와 $^{13}C-$핵자기공명스펙트럼을 분석하여 후전이금속이온 착물은 주로 리간드의 질소원자가 결합에 기여함을 알았다. Cu(Ⅱ)와 Zn(Ⅱ)이 고체착물은 원소분석, 전기전도도, 자화율 측정, 자외-가시선 및 적외선 스펙트럼분석 등으로 Cu(Ⅱ) 착물은 일그러진 팔면체, 그리고 Zn(Ⅱ) 착물은 사면체 구조를 이루고 있는 것으로 예측되었다. The stability constants$(K_f)$ of the complexes of some transition and post-transition metal ions (Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ), Pb(Ⅱ), Hg(Ⅱ)) with $N_2O_3$-donor macrocyclic ligand, 1,15-diaza-3,4 : 12,13-dibenzo-5,8,11-trioxacyclooctadecane ($NtnOdienH_4$), have been determined by potentiometry in aqueous solution at $25^{\circ}C$. Log $K_f$ values of the complexes were : Co(Ⅱ): 3.83, Ni(Ⅱ) : 4.56, Cu(Ⅱ) : 7.74, Zn(Ⅱ) : 4.98, Cd(Ⅱ) : 3.91, Pb(Ⅱ) : 6.65, and Hg(Ⅱ) : 14.87. The order of stabilities of transition metal complexes was the same as the natural order of stability proposed by Williams-Irving. In post-transition metal complexes, the order of stabilities was Cd(Ⅱ) < Pb(Ⅱ) < Hg(Ⅱ), and the covalent character in metal ion-donor atoms bonds appeared a dominant factor in the stability. In methanol solution, each metal ion forms 1 : 1 complex, while Ni(Ⅱ) ion forms both 1 : 1 and 1 : 2 complexes. It was confirmed by $^1H-$ and $^{13}C-$NMR spectral study that the nitrogen atoms in the ligand were major contributors for the complexation of post-transition metal ions with the ligand. It was shown, by elementry analysis, electrical conductivity and magnetic susceptibility measurements, and spectral analysis, that solid Cu(Ⅱ)-and Zn(Ⅱ)-complexes have a distorted octahedral and a tetrahedral structure, respectively.

PZT 세라믹의 전기광학적 특성에 관한 연구

김시중,김건,안병준,Kim Si-Joong,Kim Kun,Ahn Byeung-Joon 대한화학회 1992 대한화학회지 Vol.36 No.1

페로브스카이트구조를 갖는 $Pb(Zr_{1-y}Ti_y)O_3$ (PZT)계의 $Pb^{2+}$ 위치에 $Nd^{3+}$ 이온을 치환시키면서 그 결정구조와 결합특성을 X-선 회절분석법 및 적외선 분광광도법으로 알아보았으며, 이런 구조변화가 (Pb1-xNdx)(Zr1-yTiy)O3 (PNZT)계의 전기적 및 광학적 특성에 미치는 영향에 대하여 조사하였다. $Pb^{2+}$ 이온이 $Nd^{3+}$ 이온으로 치환될수록 정방성이 감소하며, 8${\sim}$12 mol% 치환되었을 때 입방정계의 구조이다. 결정내의 결합강도는 입방정게의 구조일 때 가장 강하고 높은 투광도를 나타냈으며, PNZT계 화합물이 투광도를 나타내는 것은 전자의 전하-이동 전이에 의한 것으로 생각된다. X-ray diffraction analysis and infrared spectrophotometry were used to investigate the crystal structures and the bonding characteristics in $Pb(Zr_{1-y}Ti_y)O_3$ (PNZT), which has a perovskite structure. As $Pb^{2+}$ of PZT was substituted by 8${\sim}$12 atom% $Nd^{3+}$ ion, the structures were changed to cubic from tetragonal and its transmission had maximum value. Transmission increased as the stretching force constant $(k_s)$ of unit cell increased. It is supposed that the electro-optic characteristics might occur due to electron-transition from HOMO to LUMO of titanium ion.

Methanol-물 및 2-Propanol-물의 混合溶媒에서의 Hydrogen Cupferrate의 酸解離常數의 決定

김시중,윤창주,장인순,Si-Joong Kim,Chang-Ju Yoon,In-Soon Chang 대한화학회 1966 대한화학회지 Vol.10 No.3

The glass electrode was empirically calibrated in methanol-and 2-propanol-water mixed solvents, by means of which the pH-meter reading could be converted to stoichiometric hydrogen ion concentration. The thermodynamic dissociation constants of hydrogen cupferrate in methanol-and 2-propanol-water solution were potentiometrically determined with the changes in composition of organic solvents at 0.01 and 0.05 of the ionic strength and 25$^{\circ}C$. The empirical formula of the constants with mole fraction (n) of the organic solvent are as follow: methanol-water solution $pK_a$= 2.24n + 4.29 at ${\mu}$ = 0.01 n = 0.0476∼0.642 $pK_a$ = 2.35n + 4.38 at ${\mu}$ = 0.05 n= 0.0446~0.642 2-propanol-water solution $pK_a$= 5.50n + 4.48 at ${\mu}$ = 0.05 n = 0.0253~0.259 The relationships between $pK_a$ of acetic acid, propionic acid and HCup and dielectric constant of some mixed solvents were discussed. It would be considered that the factors effecting $pK_a$ value of weak acid in mixed-solvent are not only dielectric constants but acid-base character and solvation effect of the solvent, etc.